Clear liquid detergent composition

ABSTRACT

A single-phase concentrated liquid detergent composition comprises (a) 7 1/2 -14% by weight of a mixture of anionic synthetic detergents, (b) 12% to the solubility limit of potassium pyro- or tripolyphosphate, (c) 3.5-6% sodium silicate solids with a SiO2:Na2O ratio of 1.6-2.6, (d) 2.5-9% of an anionic solubilizer, and (e) 40-74.5% water.  The composition preferably also contains (f) 1-6% ethanol, isopropanol, or diethylene glycol monobutyl ether, and (g) 1-3% of the mono- or diethanolamide, or of the mono- or diisopropanolamide of one or more fatty acids of the coconut group. Ingredient (a) comprises 1/7 - 3/4 potassium alkyl glyceryl ether sulphonate in which the alkyl group is at least 50% derived from alcohols of 10-14 carbon atoms, such as coconut or oxo alcohols, and this compound also comprises not less than 2% of the total composition.  The rest of the mixture (a) consists of at least one alkali metal or alkanolamine salt of an alkali-stable organic sulphuric reaction product which has a solubility of at least 4 parts in a solution consisting of 8 parts potassium alkyl glyceryl sulphonate, 20 parts potassium pyrophosphate, 6 parts sodium toluene sulphonate, 4 parts ethanol, and 50 parts water.  The sulphuric reaction products preferred are sodium and potassium polypropylenebenzene sulphonate, and potassium alkyl triethenoxy sulphate in which the alkyl group is predominantly dodecyl. Component (d), if of straight chain configuration, is a water-soluble phosphate containing 1-3 hydrophobic straight hydrocarbon chains, each having up to 5 carbon atoms in the chain; if of cyclic configuration, (d) is a sulphonate in which the hydrophobic hydrocarbon portion of the molecule contains either a benzene ring, or an alkyl-substituted benzene group of up to 8 carbon atoms. Suitable solubilizers are triamyl phosphate, or sodium benzene or xylene sulphonates, but sodium toluene sulphonate is preferred. Triethanolamine, corrosion inhibitors, substantive fluorescent agents, dyes, and perfumes may also be incorporated.  Specification 848,224 and U.S.A.  Specification 2,618,607 are referred to.

United Stat P21 t n- O F 2,877,185 CLEAR LIQUID DETERGENT COMPOSITION William C. Krumrei, Springdale, Bruce Strain, Wyoming, and Haskell J. Peddicord, Colerain Township, Hamilton County, Ohio, assignors to The Procter & Gamble Company, Cincinnati, Ohio, a corporation of Ohio No Drawing. Application June 29, 1956 Serial No. 594,696

8 Claims. (Cl. 252-137) This invention is directed at the provision of liquid The corrosion inhibitor most effective in inhibiting corrosion of aluminum by alkaline phosphates is silicate of soda. In the compositions of the prior art, the addition of silicate of soda to an aqueous solution of an anionic synthetic detergent and an alkaline phosphate caused a separation, cloudiness, or livering." This is described in U. S. Letters Patent 2,618,607, issued November 18, 1952, to Herbert L. Sanders.

Most anionic synthetic detergents are not, unassisted, completely soluble in aqueous phosphate solutions of a concentration of 18% or more, even in the absence of silicate. The anionics salt out, forming a gummy layer at the top of the solution or a two phase system. Complete solution of anionic synthetic detergent in such phosphate solutions can be achieved, however, with a solubilizer, usually a sodium salt ofthe sulfonates of benzene or methyl substituted benzene. silicate of soda, in amounts adequate to inhibit corrosion of aluminum during the use of the composition in cleansing operations, to those previously known phosphate solutions into which an anionic synthetic detergent has been thus solubilized, the silicate will not dissolve completely, but forms a gelatinous mass or a two phase system.

One of the present inventors has found, as described in the co pending application ofW. C. Krumrei, entitled Detergent Composition, Serial No. 594,676, filed June 29, 1956, that a specific anionic synthetic detergent in aqueous liquid heavy duty detergent formulations has the property of solubilizing an alkali metal silicate in amounts adequate to inhibit corrosion by phosphates. Silicate of soda is preferred but potassium silicate may be used. The specific anionic synthetic detergent is a water soluble alkyl glyceryl ether sulfonate in which the alkyl radical is derived at least 50% from alcohols of 10 to 14 carbon atoms.

A typical composition embodying this prior discovery may contain from about 6% to about 15% of salts of alkyl glyceryl ether sulfonate, 12% to 27% of potassium pyrophosphate, or potassium tripolyphosphate,2% to 6% of ethyl or isopropyl alcohol, or diethylene glycol monobutyl ether, 3.5% to 6% of silicate of soda (solids basis) of SiO :Na O ratio of 1.6:1 to 2.6:1, 3.0% to 8% of a solubilizing agent, and water to make 100%. This produces a clear solution at room temperature and remains clear down to about 50 F.

The alkyl glyceryl ether sulfonate used in both the prior discovery and in the present invention contains about 15% of diglyceryl ether sulfonates. This is only because of the ease of manufacturing this species. I The If one adds invention may be carried out with alkyl glyceryl ether,

sulfonates, where the alkyl is at least 50% radicalsof alcohols of 10 to 14 carbons, with only monoglyceryl radicals present or with up to about 30% of diglyceryl' radicals present The term alkyl glyceryl ether sulfonate as used herein means any and all of the alkyl glyceryl ether sulfonates from'those containing only monoglyceryl, radicals to those. containing up to 30% diglyceryl radicals.

The preferred alkyl glyceryl ether sulfonate is made" by reacting an alcohol or alcohol mixtures, containing at least 50% of'alkyl radicals of valcohols'of 10 to 14 carbon atoms, with from 100% to 130% of the theoretically required amount of epichlorohydrin. The alkyl chloroglyceryl ethers formed by the reaction of this alcohol and epichlorohydrin are converted to glycidyl ethers by heating with a caustic soda solution. The glycidyl ethers thus formed are sulfonated with an alkali metal bisulfite. This results in a content of alkali metal chlorides and sulfates of under 6% of the alkyl glyceryl ether alkali metal sulfonate. Low electrolyte also may be attained by purifying the conventionally Streckerized chloroethers.

Instead of the fatty alcohols used to prepare the alkyl glyceryl ether sulfonate there may be used the alcohols prepared by the 0x0 reaction from straight chain olefins. These should meet the same qualifications as to chain length as the fatty alcohols, that is, these should 1 contain at least 50% of alcohols of 10 to 14 carbons.

A number of solubilizing agents are useful in effecting complete solution of synthetic detergents in relatively concentrated electrolyte systems.

amyl phosphate, or other trialkylphosphates where the sum of the carbons in the alkyl groups are not more than 15, are etlective. The alkali metal salts of various or-.

gauic sulfonates have been used for their solubilizing properties. Petroleum sulfonate salts, salts of benzene, sulfonate and methyl substituted benzene sulfonate are among the best ofthese. The manner in which the anionics solubilize is presented in Schwartz and Perry,

Surface Active Agents, page 307 et seq., Interscience Publishers, New York, 1949.

' Generically speaking the solubilizers found useful in contain only one alkyl-substituted or unsubstituted cyclicgroup containing a total of not more than 8 carbon atoms.

The hydrophilic portion of the molecule may be either. the water soluble salt .of a sulfonic acid radical (sulfo- It is to be understood that wherever hereinafter and in the claims the term anionic,

nate) or a phosphate.

solubilizer appears amaterial coming within the scope of the above definition is'intended.

The solubilizer we prefer is sodium toluene sulfonate. Sodium benzene sulfonate and sodium xylene sulfonate are also effective but require slightly larger amountsto eifect blending. The present invention is based upon our discovery that the chill test-or resistance to clouding and separation at low temperatures-of the prior compositions described above is greatly improved by the addition of a second anionic synthetic detergent to the composition. If the alkyl glyceryl ether sulfonate is present in greater amounts than about 8% of the total.- composition, this addition'will be in the nature of a Patented Mar. 10, 1959 Trialkyl phosphates, t where the alkyl is of low molecular weight, such as tri- 3 substitution, the alkyl glyceryl ether sulfonate being reduced to about 8% to allow of the addition of the secnd anionic. If the alkyl glyceryl ether sulfonate is present in amounts of about 8% or less the second anionic may be added without reducing the alkyl glyceryl ether sulfonate.

The sum of the twoanionic synthetics is preferably not more-than about 14%. Thus, if the alkyl glyceryl ether sulfonate is at 8%, the second anionic can be 6%.

If it is desired to have the second anionic at a higher" level than 6% the alkyl glyceryl ether sulfonate should bereduced accordingly, for instance 4% alkyl glyceryl ether sulfonate and 9% of the second anionic is a satisfactory combination. The second anionic will normally be present in the amounts from A to 6 times (6:1 ratio) the amount of the alkyl. glyceryl ether sulfonate, the sum of the two being not over about 14%. The re.- mainder will be alkyl glyceryl ether sulfonate.

When these second anionics are used a coconut alkylol amide can be usedto enhance sudsing.

Example I The composition has the. formula:

Parts by wt. Potassium alkyl glyceryl ether sulfonate containing 66% of radicals from dodecyl alcohol, the remainder being alcohols of 10, 14 and 16 carbons 8 Sodium alkyl benzene sulfonate, the alkyl being polypropylene averaging about 12 carbons Potassium pyrophosphate 20 Coconut monoethanolamide 1 Ethyl alcohol- 4 Sodium toluene sulfonate 4 Sodium silicate solids of SiO /Na 0 ratio of 2.0 :1' 4 Water 54 49 parts of water were heated to about 135 F. This alcohol in this formula may be replaced by. isopropanol and equal effects obtained.

This formulation will allow of a moderate amount of variation. varied between 2 and 9 parts, the alkyl benzene sulfonate between and 5 parts, the pyrophosphate between 18 and 22 parts, the alcohol between 3 and 5 parts, the amide from 1 to 3 parts, the silicate (solids basis) between 3.5 and 6 parts and the sodium toluene sulfonate between 2.5 and 9 parts, with water to make 100 parts.

Example II The potassium alkyl glyceryl ether sulfonate was identical with that of Example I. The second anionic used was'themixture of'potassium salts of the sulfuric acid esters'of the product of the reaction of'3 moles of 'ethylene' oxide with 1 mole of middle cut coconut alcohols,

containing 66% dodecyl alcohol, the remainder of the alcohols being largely l4 and 16 carbons. This second anionic will for'convenience be'called alkyl (EtO) Sulfate. The composition. of this-example was as follows.

The sodium toluene sulfonate was- The alkyl glyceryl ether sulfonate can be Parts by wt. Potassium alkyl glyceryl ether sulfonate, containing 66% of radicals from dodecyl alcohol the remainder being alcohols of 10, 14 and 16 carbons 8 Potassium alkyl (EtO) sulfate (defined above) 4 Potassium pyrophosphate 2O Coconut monoethanolamide 1 Ethyl alcohol 4 Sodium silicate solids of ratio SiO /Na O of 2.0:1 4 Sodium toluene sulfonate -a 6 Water -a. 53

Thiscomposition was prepared by taking 48 parts of water and heating it to about 135 F. The temperature was maintained at about this point throughout the preparation. The potassium alkyl glyceryl ether sulfonate and the potassium alkyl (EtO) sulfate were dissolved in the heated water. The potassium pyrophosphate was added and dispersed. Sodium silicate solution containing 4' parts, of silicate solids and 5 parts of water was added. The coconut ethanolamide was dissolved in the alcohol and added. Then the sodium toluene sulfonate wasv added and the mixture well stirred to achieve blending. The clear solution was. then cooled to room temperature. It had good heavy duty detergent properties and did not separate when cooled to 50 F. but began to cloud at about 40 F.

This formula will allow of a moderate degree of variation. The alkyl glyceryl ether sulfonate may vary be tween 2 and 8 parts, the alkyl (EtO) sulfate from 3.5 to 4.5 parts, the pyrophosphate from 18 to 22 parts, the alcohol from 4 to 5 parts, the amide from 1 to 2.5 parts, the silicate solids from 3.5 to 5 parts and the sodium toluene sulfonate from 5 to 8 parts with water to make parts. There may be substituted for the potassium (EtO) sulfate the sodium or potassium salts of the sulfated product of the reaction, of 4 moles of ethylene oxide. with 1 mole of nonylphenol.

Example III The composition contained the following-all parts by weight:

Parts by wt.

Potassium alkyl glyceryl ether sulfonate, containing 66% of radicals from dodecyl alcohol the remainder being alcohols of 10, 14 and 16 carbons"--- 8 Potassium alkyl (EtO) sulfate, the same as in Example II 4 Potassium pyrophosphate 20 Sodium silicate. solids of ratio siO /Na O of 2:1.. 4 Coconut monoethanolamide a 1 Sodium toluene sulfonatea 6 Water a 1 57' This was prepared by taking 51 parts of wateraud heating it to about F. The temperature was maintained atabout this point'during the preparation of this example. 7

The potassium alkyl glyceryl sulfonate and the potassium alkyl (EtO) sulfate were added and dissolved by stirring. The potassium pyrophosphate was added and stirred. The silicate, containing 5 parts of water, and the amide were added and stirred. The sodium toluene sulfonate was addedand stirred to blend'the mixture. Upon cooling to room temperature a clear solution was obtained. Thishad good sudsing and detergent properties. The viscosity and chill resistance can be improved" by the substitution of assistant solubilizers such as ethyl or isopropyl alcohol or diethylene glycol monobutyl ether for a portion of the water.

Example IV Potassium tripolyphosphate may be used in place of" Y I v Partsbywt. Potassium alkyl glyceryl ether sulfonate, containing 66% of radicals from dodecyl alcohol, the remainder being alcohols of 10, 14 and 16 carbons 8 Sodium alkyl benzene sulfonate, the alkyl being polypropylene averaging about 12 carbons 5 Coconut monoethanolamide 1 Potassium tripolyphosphate Sodium silicate of soda solids of SiO /Na O ratio of 1.6:1 to 2.6:1 4 Ethyl alcohol 4 Sodium toluene sulfonate 4 Water.. 60

55 parts of water were heated to about 135 F. and the ingredients added as shown in Example II, the alkyl benzene sulfonate taking the place of the alkyl (EtO) sulfate. Five parts of Water were added with the silicate solids to make the 60 parts shown in the formula.

This was a clear solution, not clouding or settling out at 50 F., but tending to cloud at about 40 F. The ethyl alcohol in this formula may be replaced by diethylene glycol monobutyl ether and equal results obtained.

The temperature of mixing need not be maintained at the 135 F. shown. 110 F. to 140 F. is preferred but somewhat higher or lower temperatures are not objectionable.

It is obvious that the builder need not be a single phosphate, a mixture of potassium pyrophosphate and potassium tripolyphosphate can be used.

Potassium toluene sulfonate 8.5 Ethyl alcohol 4 Potassium pyrophosphate 1% Coconut monoethanolamide 3 Sodium silicate solids of SiO /Na O ratio of l.6 4.25 Triethanolamine- 1.0 Corrosion inhibitors, substantive fluorescers, dyes and perfume 1.3

Water to make 100 parts (5.3 parts water in 4.25

silicate solids) 46.95

This was prepared by heating 41.65 parts of water to about 135 F. and the ingredients added with good stirring, in the following order. The alkyl glyceryl ether sulfonate and the alkyl benzene sulfonate; the potassium toluene sulfonate; the alcohol in which was dissolved the amide and the substantive fiuorescers; the potassium pyrophosphate; the triethanolamine; the silicates, the inhibitors. After cooling, the perfume and color was added.

The order of addition is not critical, it can be varied. There is one point, however, that should be observedthe silicate should go into the mixture after the phosphate. The relatively high alkalinity of the phosphate is needed to keep the silicate from jelling. This composition had good detergent qualities and was clear down to about 40 F.

If alkyl glyceryl ether sulfonate is not used in the formulations of the above examples, all of the synthetic detergent being the second anionic, a clear single phase solution is not attained. If, for instance, alkyl benzene sulfonate, where the alkyl is polypropylene averaging about 12 carbons, is the sole anionic used in these formulations, the addition of alcohol causes two clear layers to form, but they will not blend into a single phase solution, upon the addition of a solubilizer. If an alkyl (EtO); sulfate, where the alkyl is middle cut coconut alcohol containing about 65% of radicals from dodecanol is used as the sole anionic, the same phenomenon occurs.

A convenient test for clarity may be made by placing the preparation in a test tube 20 mm. diameter and mm. long and holding for five days at some selected temperature below room temperature. In this test highly satisfactory compositions will not cause the alkyl glyceryl ether sulfonate to salt in a viscous or jcll-like layer at the top, nor separate into two layers. The detergent of the present invention rates as highly satisfactory at room temperatures down to about 40 F., whereas the preparations with alkyl glyceryl ether sulfonate as the sole anionic will withstand temperatures down to about 50 F. only.

Ordinary visual observation in good light, as looking toward a window is used to determine the state of the preparation.

The examples show how the basic discovery-that a mixture of alkyl glyceryl ether sulfonate and a second anionic will solubilize silicate in phosphate solutionsmay be used to prepare liquid heavy duty synthetic detergents which remain clear when cooled down to about 40 F. These preparations retain practically all of the other advantages of straight alkyl glyceryl ether sulfonate liquid detergents, particularly the dispersal of soil, thus minimizing redeposition of soil upon the clothes.

It will be noted that alkyl benzene sulfonate is used as the sodium salt and the alkyl (EtO) sulfate as the potassium salt. These salts are preferred because each is the more soluble salt of the respective anionic synthetic detergent. There is required in these formulations some control of the mole ratio of potassium to sodium to prevent crystal formulations; also, a maximum sodium ion concentration of about 1.9% of the total composition is the upper limit to prevent sodium pyrophosphate crystals from forming. When the second anionic is used as the sodium salt, with the silicate and solubilizer as sodium salts, the mole ratio of potassium to sodium is about 3.4 to 1. Where all of the composition, except the silicate, is present as potassium salts-the silicate being sodiumthe mole ratio of potassium. to sodium is about 6.9 to 1. The preferred molar ratios of potassium to sodium are then from about 3 to 1, to 7 to 1.

The alkylol amides added as suds builders can be made from the fatty acids of any of the oils of the coconut group comprising coconut oil, palm kernel oil, babassu oil and oils of other members of the tropical palm group that contain at least 50% of lauric and myristic acids. They can also be made from middle cut fractions of the fatty acids of these oils that have their lauric content raised by distillation. If high sudsing is not requiredthe amides may be omitted from the compositions, but with some sacrifice in sudsing power.

The silicate and the alkali toluene sulfonate can be added as the sodium salts. Some sodium ions are desirable, although a heavy duty liquid synthetic detergent may be formulated with all of the cations potassium. The preferred formulation will have at least the silicate present as the sodium salt.

It will be understood that coloring matter, fabric substantive fluorescent dyes and tarnish inhibitors may be added at any convenient point in the mixing of the composition, and that perfume may be added after the composition has been prepared and cooled.

The formulas may be varied somewhat from those given in the examples. It will be apparent that the potassium alkyl glyceryl ether sulfonate is the solubilizer for the silicate. Up to 6% silicate solids can be kept in clear solution by formulations as shown in the examples, containing alkyl glyceryl ether sulfonate and potassium pyro-' phosphate. There is no point in going below 3.5% silicate solids as inhibition of corrosion becomes inadequate below this point. The silicate can have a ratio of SiO /Na O of 1.6 to 1 to 2.6 to 1. Lower ratios become too alkaline and higher ratios are difiicult to dissolve.

The 'solubilizing power of alkyl. glyceryl ether 'sulfonate is exerted upon the phosphates as well as the silicates. The potassium pyrophosphate or potassium tripolyphose phate may be used in an amount from a minimum of 12 parts to a maximum of the limit of solubility at room temperature of the phosphate in the complete detergent. This maximum limit on the amount of phosphate depends upon the amount of the second anionic used. When a heavy duty liquid detergent is prepared with alkyl glyceryl ether sulfonate as the sole anionic (and with added solubilizing agents), parts of potassium pyrophosphate could be dissolved in a composition containing 50 parts of water and 12 parts of alkyl glyceryl ether sulfonate. When 4 of the 12 parts of alkyl glyceryl ether sulfonate in the above solution are replaced by 5 parts of alkyl benzene sulfonate the solubility of the potassium phosphates is reduced to about 23 parts. Our preferred phosphate is pyrophosphate'because of the greater solubility and stability of this phosphate.

Coconut amides may be monoor diethanol, propanol or isopropanol and can be tolerated from the standpoint of freeze recovery up to about 3%. Below 1% they do. not accomplish much enhancement of sudsing.

The alcohols, ethanol or isopropanol, or diethylene glycol monobutyl ether, used to dissolve the amide, to reduce viscosity and to act as assistant solubilizers are preferably used from about 1% to about 6%. Alcohol promotes blending and lowers viscosity, but more than 6% causes a tendency to separation. With a longer time spent in blending, alcohol may be omitted, and a satis factory heavy duty liquid detergent can be produced.

The sodium toluene sulfonate, benzene sulfonate oixylene sulfon'ate may be used between 2.5% and 9%.

The amount of alklyl 'glyceryl 'sulfonate must be at least 2% in the compositions like those shown in the examples to solubili z e the silicate, that is, it will be as a minimum, of the total anionic synthetic detergent. Moreover, the minimum amount of alkyl glyceryl ether sulfonate that will prevent redeposition of soil is about 2%. The amount of alkyl glyceryl ether sulfonate may go as high as 14, but at the expense of clarity at low temperatures. The preferred range is 4% to 8%, with the second anionic being present at 9% to 5%. With the second anionic at A the alkyl glyceryl ether sulfonate, the minimum amount of anionic synthetic detergent in the compositions of this invention will be 7 /2%.

Alkyl (EtO) sulfate was used as the second anionic detergent in Example III. In the reaction between a high molecular alcohol and n-moles of ethylene oxide per mole of alcohol the species produced not all contain nmoles of ethylene oxide. The species will vary from 11:0 to those wherein the polyethylene oxide is at least Zn in polymerization. For this reason there is nothing specific about reacting'exactly '3 moles of ethylene oxide. The sulfated reaction products of 2 moles of ethylene oxide and of 4 moles of ethylene oxide with a given fatty alcohol will differ only slightly from alkyl (EtO) sulfate, and may be used interchangeably. As moles of EtO increase, electrolyte compatibility decreases and chill improves.

The water will preferably be not less than about 40%, as this much is required to solubilize the ingredients. The water used will not exceed 75%, of the total com position if the product is to be called concentrated.

Other anionic detergents than alkyl benzene sulfonate, sulfated alkyl ethylene oxide condenses, and sulfated nonylphenol ethylene oxide condensates may be used as second anionics. The anionic sulfuric organic reaction prod-V ucts which "are preferred are those which have sodium or potassium or'substitutedammonium salts which have a solubility of at least 4, parts in parts of Water in which is dissolved 8 parts of potassium alkyl glyceryl ether sulfonate and'20 parts of potassium pyrophosphate with 6 parts of sodium toluene sulfonate'and -4 parts of ethyl alcohol; and whichdonut-hydrolyze in alkaline aqueous 8 solution. Stability in alkaline aqueous solutions is essential for every constituent.

What is claimed is:

1. A substantially clear concentrated liquid detergent composition consisting essentially of, in parts by weight: (a) 7 /2 parts to 14 parts of anionic synthetic detergents of which not less than 2 parts and not more than is potassium salts of alkyl glyceryl ether sulfonate, said alkyl containing at least 50% of radicals from alcohols of 10 to 14 carbon atoms, the remainder of the anionic synthetic detergent being an alkaline-stable organic sulfuric reaction product the alkali metal and alkylol amine salts of which are characterized by a solubility of at least 4 parts in a solution consisting of 8 parts of said potassium alkyl glyceryl ether sulfonate and 20 parts of potassium pyrcphosphtae in 50 parts of water with 6 parts of sodium toluene sulfonate and 4 parts of'ethyl alcohol, said organic sulfuric reaction product being stable in aqueous alkaline solution; (b) a phosphate selected from the group consisting of potassium tripolyphosphate and potassium pyrophosphate and mixtures therof, in an amount from a minimum of 12 parts to the limit of solubility at room ternerature of said potassium phosphate in the complete detergent; (c) 3.5 parts to 6 parts of sodium silicate solids of SiO /Na O ratio of 1.611 to (2.611; (d) 2.5 parts to 9 parts of an anionic solubilizer selected from the group consisting of trialkyl phosphates wherein each of the alkyl groups contains not more than 5 carbon atoms, the alkali metal salts of benzene sulfonate, the alkali metal salts of toluene sulfonatc and the alkali metal salts of xylene sulfonate; (e) 40 to 75 parts of water, to bring the total of all components to parts.

2. A substantially clear concentrated liquid detergent composition consisting essentially of, in parts by Weight; (a) 7% to 14 parts of anionic synthetic detergents of which not less than 2 parts and not more than 75% is potassium salt of alkyl glyccryl ether sulfonate, said alkyl containing at least 50% of radicals from alcohols of 10 to 1 4 carbons, the remainder of the anionic syn thetic detergent being an organic sulfuric reaction product the alkali metal and alkylol amine salts of which are characterized by'a solubility of at least 4 parts in a solution of 8 parts of said potassium alkyl glyceryl ether sulfonate and 20 parts of. potassium pyrophosphate in 50 parts of water with 6 parts of sodium toluene sulfonate and 4 parts of ethyl alcohol, said organic sulfuric reaction product being stable in alkaline aqueous solution; (b) a potassium phosphate selected from the group consisting of potassium tripolyphosphate and potassium pyrophosphate and mixtures thereof, from a minimum of 12 parts to the maximum of the'limit of solubility at room temperature of said potassium phosphate in the complete detergent; (c) 1 to 6 parts of assistant solubilizers selected from the group consisting of ethyl alcohol, isopropyl alcohol, and diethylene glycol monobutyl ether; (d) 1.0 parts to 3.0 parts of alkylol amide of fatty acids of the coconut group, said alkylols being selected from the group consisting of monoethanol, diethanol, monoisopropanol, and di-' opropanol; (e) 3.5 parts to 6 parts of sodium silicate solids of SiO /Na O ratio of 1.6:1 to 2.621; (f) 2.5 parts to 9 parts of an anionic solubilizer selected from the group consisting of trialkyl phosphates wherein each of the alkyl groups contains not more than 5 carbon atoms, the alkali metal salts of benzene sulfonate, the alkali metal salts of toluene sulfonate and the alkali metal salts of xylene sulfonate; (g) Water to make 100 parts but not less than about 40 parts.

3. The liquid detergent composition of claim 2 con taining about 8 parts of the potassium alkyl glyceryl sulfonate; about 5 parts of the alkali metal salt of alkyl benzene sulfonate, about 20 parts of potassium pyrophosphate, about 4 parts of the alcohol, about 1 part of'the alkylol amide, about 4 parts .ofthe sodium silicate solids and about 4 parts of sodium toluene sulfonate, sufficient water being present to bring the total of all components to 100 parts.

4. A substantially clear concentrated liquid detergent composition consisting essentially of, in parts by weight, 2 to 9 parts of the potassium salts of alkyl glyceryl ether sulfonate, at least 50% of the alkyl groups of the said alkyl glyceryl ether sulfonate being derived from alcohols having from 10 to 14 carbon atoms, 4 to 9 parts of alkali metal alkyl benzene sulfonate, the alkyl group of which averages about 12 carbon atoms, the sum of the said salts of alkyl glyceryl ether sulfonate and alkali metal alkyl benzene sulfonate being not more than 14 parts, 18 to 22 parts of potassium pyrophosphate, 3 to 5 parts of ethyl alcohol, 1 to 2 parts of alkylol amides of the fatty acids derived from oils of the coconut group, the alkylol portion of the said amides being selected from the group consisting of monoethanol, diethanol, monoisopropanol and diisopropanol, 3.5 to 6 parts of sodium silicate solids having an SiO /Na O ratio of from 1.6:1 to 26:1, 2.5 to 9 parts of sodium toluene sulfonate and not less than 40 parts of water and sufficient to bring the total of all components to 100 parts.

5. A substantially clear concentrated liquid detergent composition consisting essentially of, in parts by weight, 2 to 9 parts of the potassium salts of alkyl glyceryl ether sulfonate, at least 50% of the alkyl groups of the said alkyl glyceryl ether sulfonate being derived from alcohols having from 10 to 14 carbon atoms, 4 to 9 parts of alkali metal alkyl benzene sulfonate, the alkyl group of which averages about 12 carbon atoms, the sum of the said salts of alkyl glyceryl ether sulfonate and alkali metal alkyl benzene sulfonate being not more than 14 parts, 18 to 22 parts of potassium pyrophosphate, 3 to 5 parts of isopropyl alcohol, 1 to 2 parts of alkylol amides of the fatty acids derived from oils of the coconut group, the alkylol portion of the said amides being selected from the group consisting of monoethanol, diethanol, monoisopropanol and diisopropanol, 3.5 to 6 parts of sodium silicate solids having an SiO /Na ratio of from 1.6:1 to 2.621, 2.5 to 9 parts of sodium toluene sulfontae and not less than 40 parts of water and sufficient to bring the total of all components to 100 parts.

6. A substantially clear concentrated liquid detergent composition consisting essentially of, in parts by weight, 4 to 8 parts of the potassium salts of alkyl glyceryl ether sulfonates, at least 50% of the alkyl groups of the said alkyl glyceryl ether sulfonates being derived from alcohols having from 10 to 14 carbon atoms, 3.5 to 4.5 parts of the potassium salts of the sulfated reaction product of from 2 to 4 moles of ethylene oxide with 1 mole of a mixture of fatty alcohols, at least 50% of the mixture of said fatty alcohols being fatty alcohols containing from 10 to 14 carbon atoms, 18 to 22 parts of potassium pyrophosphate, 4 to parts of ethyl alcohol, 1.5 to 2.5 parts of alkylol amides of the fatty acids derived from oils of the coconut group, the alkylol portion of the said amides being selected from the group consisting of monoethanol, diethanol, monoisopropanol and diisopropanol, 3 to 5 parts of sodium silicate solids having an SiO /Na O ratio of from 1.6:1 to 2.6:1, 5 to 8 parts of sodium toluene sulfonate and not less than parts of water and sufficient to bring the total of all components to parts.

7. A substantially clear concentrated liquid detergent composition consisting essentially of, in parts by weight, 4 to 8 parts of the potassium salts of alkyl glyceryl ether sulfonates, at least 50% of the alkyl groups of the said alkyl glyceryl ether sulfonate being derived from alcohols having from 10 to 14 carbon atoms, 3.5 to 4.5 parts of the potassium salts of the sulfated reaction product of from 2 to 4 moles of ethylene oxide with 1 mole of a mixture of fatty alcohols, at least 50% of the mixture of said fatty alcohols being fatty alcohols containing from 10 to 14 carbon atoms, 18 to 22 parts of potassium pyrophosphate, 4 to 5 parts of isopropyl alcohol, 1.5 to 2.5 parts of alkylol amides of the fatty acids derived from oils of the coconut group, the alkylol portion of the said amides being selected from the group consisting of monoethanol, diethanol, monoisopropanol and diisopropanol, 3 to 5 parts of sodium silicate solids having an SiO /Na O ratio of from 1.6:1 to 2.611, 5 to 8 parts of sodium toluene sulfonate and not less than 50 parts of water and sufiicient to bring the total of all components to 100 parts.

8. A substantially clear concentrated liquid detergent composition consisting essentially of, in parts by weight, 8 parts of the potassium salts of alkyl glyceryl ether sulfonate, at least 50% of the alkyl groups of the said alkyl glyceryl ether sulfonate being derived from alcohols having from 10 to 14 carbon atoms, 4 parts of the potassium salts of the sulfated reaction product of 3 moles of ethylene oxide with 1 mole of a mixture of fatty alcohols, at least 50% of said mixture of fatty alcohols being fatty alcohols containing from 10 to 14 carbon atoms, 20 parts of potassium pyrophosphate, 4 parts of ethyl alcohol, 4 parts of sodium silicate solids having a. SiO /Na- O ratio of 1.6:1 to 26:1, 1.5 to 2.5 parts of alkylol amides of the fatty acids derived from oils of the coconut group, the alkylol portion of the said amides being selected from the group consisting of monoethanol, diethanol, monoisopropanol and diisopropanol, 6 parts of sodium toluene sulfonate and water in an amount sufficient to bring the total of all components to 100 parts.

References Cited in the file of this patent UNITED STATES PATENTS 2,477,383 Lewis July 26, 1949 2,581,677 Machlis Jan. 8, 1952 2,618,607 Sanders Nov. 18, 1952 2,757,143 Katzman July 31, 1956 FOREIGN PATENTS 424,596 Great Britain Feb. 25, 1935 

2. A SUBSTANTIALLY CLEAR CONCENTRATED LIQUID DETERGENT COMPOSITION CONSISTING ESSENTIALLY OF, IN PARTS OF WEIGHT: (A) 7 1/2 TO 14 PARTS OF ANIONIC SYNTKHETIC DETERGENTS OF WHICH NOT LESS THAN 2 PARTS AND NOT MORE THAN 75% IS POTASSIUM SALT OF ALKYL GLYCERYL ETHER SULFONATE, SAID ALKYL CONTAINING AT LEAST 50% OF RADICALS FROM ALCOHOLS OF 10 TO 14 CARBONS, THE REMAINDER OF THE ANIONIC SYNTHETIC DETERGENT BEING AN ORGANIC SULFRUIC REACTION PRODUCT THE ALKALI METAL AND ALKYLOL AMINE SALTS OF WHICH ARE CHARACTERIZED BY A SOLUBILITY OF AT LEAST 4 PARTS IN A SOLUTION OF 8 PARTS OF SAID POTASSIUM ALKYL GLYCERYL ETHER SULFONATE AND 20 PARTS OF POTASSIUM PYROPHOSPHATE IN 50 PARTS OF WATER WITH 6 PARTS OF SODIUM TOLUENE SULFONATE AND 4 PARTS OF ETHYL ALOCHOL, SAID ORGANIC SULFURIC REACTION PRODUCT BEING STABLE IN ALKALINE AQUEOUS SOLUTION; (B) A POTASSIUM PHOSPHATE SELECTED FROM THE GROUP CONSISTING OF POTASSIUM TRIPOLYPHOSPHATE AND POTASSIUM PYROPHOSPHATE AND MIXTURES THEREOF, FROM A MINIMUM OF 12 PARTS TO THE MAXIMUM OF THE LIMIT OF SOLUBILITY AT ROOM TEMPERATURE OF SAID POTASSIUM PHOSPHATE IN THE COMPLETE DETERGENT; (C) 1 TO 6 PARTS OF ASSISTANT SOLUBILIZERS SELECTED FROM THE GROUP CONSISTING OF ETHYL ALCOHOL, ISOPROPL ALCOHOL, AND DIETHYLENE GLYCOL MONOBUTYL ETHER; (D) 1.0 PARTS TQ 3.0 PARTS OF ALKYOL AMIDE OF FATTY ACIDS OF THE COCONUT GROUP, SAID ALKYLOS BEING SELECTED FROM THE GROUP CONSISTING OF MONOTHANOL, DIETHANOL, MONOISOPROPANOL, AND DI-IDOPROPANOL; (E) 3.5 PARTS TO 6 PARTS OF SODIUM SILICATE SOLIDS OF SIO2/NA2O RATIO OF 1.6:1; (F) 2.5 PARTS TO 9 PARTS OF AN ANIONIC SOLUBILZER SELECTED FROM THE GROUP CONSISTING OF TRIALKYL PHOSPHATES WHEREIN EACH OF THE ALKYL GROUPS CONTAINS NOT MORE THAN 5 CARBON ATOMS, THE ALKALI METAL SALTS OF BENZENE SULFONATE, THE ALKALI METAL SALTS OF TOLUENE SULFONATE AND THE ALKALI METAL SALTS OF ZYLENE SULFONATE; (G) WATER TO MAKE 100 PARTS BUT NOT LESS THAN ABOUT 40 PARTS. 